Electrode for primary batteries



A. r-lsczl-nasAc'l-l` ETAL ELECTRODE FOR PRIMARY BATTERIES oct, 2o, 1953 Filed Sept. 25, 1951 FIG. 3

INVENTORS ADOLPH FISCHBACH FREDERICK HOCHBERG BY Patented Oct. 20, 1953 ELEc'moDE 1101; PRIMARY BATTERIES Adolphv Fischbach, Allenhurst, and Frederick Hochberg, Red Bank, N. J., assignors to the United States of America as represented by the Secretary of the Army Application September 25, 1951, Serial N o. 248,261

(Cl. 13G-126) (Granted under Title 35, U. S. Code (1952),

seo. 266) n I 3 Claims.

The invention described herein may be manufactured and used by or for the Government for governmental purposes without the payment of any royalty thereon.

'This invention relates to porous Zinc-cadmium electrodes for primary batteries and to methods of making such electrodes.

It is a general object of this invention to produce a lightweight, porous, Zinc-cadmium elec trode of Agreatly improved mechanical strength which electrode may be used as a negative electrode in various electro-chemical systems provid* ing in each case a battery of high capacity per unit of weight and volume, high discharge rate and excellent operating characteristics at temperatures as low as 70 F. VvAs against the porous zinc electrode described in our copending application, Serial No. 233,928, filed June 27, i951, now Patent No. 2,640,864, the present zinccadmium electrode exhibits various improvements particularly with respect to mechanical strength, ease of manufacture and better handling in mass production.

The invention will become more apparent from the following description and raccompanying drawing of a multiple cell, deferred action type (dunk-type) meteorological battery in which V zinc-cadmium electrodes according to the invention are used as negative electrodes.

In the drawings:

Fig. 1 is an elevational view of an electrode according to the invention with the active electrodic material partly removed.

Fig. 2 is an enlarged sectional view taken along line X-X of Fig. 3 which is a top view of a dunktype battery consisting of three cells.

Referring to Fig. 1 the grid 22 consists of a gauze, net or screen made of very thin metal wire such as copper, silver, nickel, aluminum or the like. This screen wire may be as thin as 0.01 or less. The thickness of a screen is about double the thickness of the wire used to weave the screen; it is, however, possible to press the woven screen down almost to the thickness of a single wire. If, therefore, extremely thin grids are required, the screens are pressed after weaving. Various wire screens, e. g., 16/16 or 45/45 mesh, using various thicknesses up to 0.02 and more have been satisfactorily used. Finished pasted electrodes, with less than about 0.04 thickness and of extremely light weight can thus be made.

If copper wire is used it is advantageous to electro-plate the wire with a protecting and impervious coating of lead, manganese or preferably zinc or cadmium which coatings prevent corrosion or dissolution Yof the .screen metalby the electrolyte. If the battery is to be used as a one-shot battery (which is discarded after initial use) the copper wide does not have to be coated. However, where the battery is expected .to have good charge retention after activation it is betterV to protect the grid material. The screen may or may not be pressed before the protective coating isputon. r In preparing the porous zinc-cadmium electrode according to the invention a-paste is .pre.- pared by mixing the oxides of zinc and cadmium (both preferably chemically pure) .with water. The mixture `of the oxides of cadmium and zinc may contain between 5 to 50% cadmium.v This mixture is now pasted into the grids and the pasted plates are then air orroven dried. After drying they may be exposed to heat for a very short time (l0 to r15 seconds) at temperatures of about 500 to '700 C. to harden the surface of the paste so as to prevent shedding ofthe oxides on subsequent immersion into the forming solution. The forming of the plate electrodes with or without said heat treatment of the surface is preferably, carriedV out in dilute alkaline solution.

- treatment may be used which brings the plate near to the original thickness. The plate is then thoroughly washed to remove the forming solution and is then air or oven dried.

The porous zinc-cadmium electrode made according to the invention may be used as a negative electrode in combination with various electro-chemical systems and suitable acid or alkaline electrolytes. It may, for instance, be used with a silver peroxide or mercurio oxide counterelectrode and potassium hydroxide as electrolyte; or it may be used with a lead peroxide counterelectrode with sulphuric acid or uorboric acid as electrolyte. In any such combination the porous zinc plate furnishes batteries of relatively high capacity and high discharge rates at temperatures as low as F.

The new porous zinc-cadmium electrode is particularly suitable for meteorological batteries of the deferred action type as illustrated in Figs. 2 and 3 which show a dunk-type battery consisting of three cells. Each of the three cells comprises two thin, flat plate electrodes, one a negative electrede I consisting of spongy zinc-cadmium made according to the invention and the other a positive lead peroxide electrode 2. A spacer 3 of bibulous 'sheetanaterialsurrounds both electrodes laterally, .ithns.,separating the electrodes l., 2 from each other and from the insulating sheet material which constitutes the hull 4 of the cell. This hull or cell container 4 holds the elements of the electrode-spacer structure laterally 'together under pressure contact butleavesitopand bottom of the electrode-spacerfstructureopen. The bibulous spacer 3 may consist lpaper., `Woodpulp, microporous rubber, glass Wool or other liquid retaining materials, vinert to .the .action ,of the acid electrolyte. The thickness ofthe spacer 3 is designed to soak up enough electrolyte not shown) to allow complete utilization of the active material of the electrodes l, 2.

'I'he cell hull I consists of suitable plastic sheet material such as polystyrene, various poly-vinyl resins, :synthetic rubber yor other elastomers, Scotch itape, etc. AA :plurality of :such cells in .juxtaposition can be easily andtightly packaged, 'Iorinstanca in an open Trame structure or Abatftery frame .5 vwhichsurrounds the cells'laterally '.andis :of 'such :inner dimensions that'the desired number of Vcells are closely and `immovably fhe'ld `together. "The Vbattery frame 5 .may consist `vof any of the materials used for the cell hull l as -enumerated :'above.

negative .electrode of 'the other end ycell each vbeing provided, respectively. with a positive .ter- Lminal V1:1 and a negative terminal l2.

Ya lm '20 `of lwater frepellent substance, e. g., pe-

troleum jelly, silicone resinsor thelike'ispainted -on the lower'portions of the sheet `material con- :stituting the cell container l. 'This -lm I2l! pre- Metal 'tabs I0 .electrically connect ,successive Icells Vin conventional manner; Athe `positive electrode .of .one end cell yand the vents leakage currents which otherwise would follow the electrolyte film accumulated on the lower edges of the hull 4.

The .porous zinc-cadmium .eiectrode according tto vthe invention, 4whether it be'used inthe abovedescribed battery or in any other suitable battery, zwill show in addition to its excellent electric characteristics a relatively very high mechanical strength.

What yis claimed `is:

51. A Ymethod Yof Vmaking an extremely light# weight, ripercus, :cinc-cadmium negative electrode of -.hig'h :mechanical strength for primary radio sonde batteries in which the negative electrode 'is made by pasting the active material into a supporting grid and subsequent fdrying and forming the pasted electrode characterized by making 'a -pasty mixture of zinc oxide, cadmium oxide and water, pasting said mixture into a supporting metal screen, drying said pasted plate electrode and formingfit cathodically rin a forming-.solution to obtain a mixture `of sponge zinc and .sponge cadmium and vfinally washing and ldrying tsaid porous zinc-cadmium electrode.

2. A method of 'making an electrode according to claim l in which said pasted and dried `plate electrode is submitted for a very shortitim'e .to temperatures above 300 C.

3. A method of making electrodes according to claim 1 in which the pasty :mixture "craint: oxide and cadmium oxide contains between about 5 kto 50% cadmium.

ADOLPI-I FISCHBACH. FREDERICK HOCHBERG.

References Cited in the file of 'this rpatent UNITED STATES PATENTS ANumber Name Date 294,464 Haid Mar. 4, 1884 `'745,588 Ford Dec. 1, `1903 945,243 Morrison Jan. 4, .1910

1,304,852 Chamberlain May v27, 1919 1,451,801 Angell Apr. 17,1923

.12,254,286 Hauel Sept. 2, 1941 FOREIGN PATENTS Number Country .Date

353,425 France July 31, 1906 

1. A METHOD OF MAKING AN EXTREMELY LIGHTWEIGHT, POROUS, ZINC-CADMIUM NEGATIVE ELECTRODE OF HIGH MECHANICAL STRENGTH FOR PRIMARY RADIO SONDE BATTERIES IN WHICH THE NEGATIVE ELECTRODE IS MADE BY PASTING THE ACTIVE MATERIAL INTO A SUPPORTING GRID AND SUBSEQUENT DRYING AND FORMING THE PASTED ELECTRODE CHARACTERIZED BY MAKING A PASTY MIXTURE OF ZINC OXIDE, CADMIUM OXIDE AND WATER, PASTING SAID MIXTURE INTO A SUPPORTING METAL SCREEN, DRYING SAID PASTED PLATE ELECTRODE AND FORMING IT CATHODICALLY IN A FORMING SOLUTION TO OBTAIN A MIXTURE OF SPONGE ZINCE AND SPONGE CADMIUM AND FINALLY WASHING AND DRYING SAID POROUS ZINC-CADMIUM ELECTRODE. 